CN103911144A - Europium ion-doped high-molecular fluorescent encoding microsphere and preparation method thereof - Google Patents

Abstract

The invention relates to a europium ion-doped high-molecular fluorescent encoding microsphere and a preparation method thereof. The fluorescent encoding microsphere has an average particle size of 5 to 10 mu m, maximum excitation wavelength of about 300 to 350 nm and maximum emission wavelength nearby 395 to 611 nm, respectively. The preparation method comprises the following steps: dispersing surface sulfonated polystyrene-divinyl benzene cross-linking (PDSVB) microspheres in a mixed solvent and adding a Eu<3+> solution, wherein a mass ratio of the microspheres to Eu<3+> is 24:1 to 480: 1; and carrying out vibration treatment at a temperature of 70 to 90 DEG C for 0.5 to 5 h and then carrying out centrifugal washing and freeze drying so as to obtain the europium ion-doped high-molecular fluorescent encoding microsphere. According to the invention, through changing addition amounts of europium ions, a series of fluorescent encoding microspheres with different europium ion-PDSVB microsphere fluorescence-emission intensity ratios are prepared and can be used in fields like biological detection and medical diagnosis.

Description

Polymer fluorescently encoded microspheres doped with europium ions and preparation method thereof

technical field

The invention relates to a polymer fluorescent coded microsphere and its preparation method, in particular to doping with different amounts of europium ions to obtain the fluorescence emission intensity of a series of different europium ions and polystyrene-divinylbenzene cross-linked (PSDVB) microspheres The invention relates to a specific fluorescent coded microsphere, which belongs to the technical field of luminescent materials.

Background technique

Rare earth elements have unique luminescent properties and have been developed as a variety of important luminescent materials, and europium is a typical representative. Europium ions can emit a rich fluorescence spectrum after being excited, and can emit electromagnetic radiation of various wavelengths from ultraviolet to infrared. Typical red fluorescence around 611nm.

Some functionalized substrates can be successfully obtained by doping europium ions into some substrates. Literature ( Colloids and Surfaces A: Physicochem. Eng. Aspects 326 (2008) 109–114) reported doping europium ions onto inorganic silicon spheres to obtain europium-doped inorganic fluorescent silicon spheres. The ions are doped onto the inorganic silicon spheres, and the particle size of the obtained silicon spheres is not uniform. Literature ( J. AM. CHEM. SOC. 2009, 131, 15276–15283) reported that europium ions were firstly formed into chelates with organic molecules, and then doped onto polystyrene microspheres to obtain europium-doped fluorescent microspheres. ball. The experimental conditions of this method are cumbersome, and the europium ion chelate must be prepared first, and the workload is heavy.

Before the present invention was made, Suzhou Nanomicrobe Technology Co., Ltd. produced and sold a surface sulfonated polystyrene-divinylbenzene cross-linked (PSDVB) microsphere with a maximum excitation wavelength of about 330 (300-350 nm), and the maximum emission wavelength is around 395 nm. The microsphere has only one emission wavelength after being excited, and cannot be used for fluorescence encoding. It can only be used as a simple matrix sphere, and its application range is limited.

Contents of the invention

The problem to be solved in the present invention is to provide a polymer fluorescent microsphere doped with europium ions that has a simple preparation process, stable product structure and good shape in view of the shortcomings of europium-doped fluorescent microspheres in the prior art. The provided microspheres can simultaneously emit two types of fluorescence after being excited, and a series of fluorescent coded microspheres with different fluorescence emission intensity ratios of europium ions and PSDVB microspheres are prepared by changing the amount of europium ions added.

The technical solution for realizing the purpose of the present invention is to provide a polymer fluorescent coded microsphere doped with europium ions, which has an average particle diameter of 5-10 μM, a maximum excitation wavelength of 300-350 nm, and a maximum emission wavelength of 395 nm and 611 nm respectively. nearby.

The technical solution of the present invention also includes a method for preparing polymer fluorescently encoded microspheres doped with europium ions as described above, comprising the following steps:

1. Dissolve Eu ₂ O ₃ in CH ₃ COOH and make Eu ³⁺ solution with deionized water;

2. Using polyvinylpyrrolidone as a dispersant, disperse the surface sulfonated polystyrene-divinylbenzene crosslinked microspheres in a mixed solvent, the mixed solvent is by volume, isopropanol: to Ionized water=1:1, the concentration of europium ions in the mixed solvent is 3.8×10 ^-3 ~7.6×10 ^-2 mg/mL; add the Eu ³⁺ solution obtained in step (1), the microspheres and Eu ³⁺ The mass ratio is 24:1-480:1; shaking treatment for 0.5-5 hours at a temperature of 70-90° C., centrifugation washing, and freeze-drying to obtain europium-doped polymer fluorescence-encoded microspheres.

Compared with prior art, the beneficial effect of the present invention is:

1. The present invention adopts the pre-prepared europium ion solution, doping europium into the microspheres in the form of ions, and prepares a method for fluorescently encoded microspheres with good surface morphology. This technical solution does not involve chemical reactions, so the process is simple , easy to operate and suitable for industrial production.

3. The present invention prepares a series of fluorescent coded microspheres with different fluorescence emission intensity ratios (I ₂ /I ₁ ) between europium ions and PSDVB microspheres by changing the amount of europium ions added, which can be applied to fields such as biological detection and medical diagnosis , where I ₁ is the fluorescence emission intensity of PSDVB microspheres, and I ₂ is the fluorescence emission intensity of europium ions.

Description of drawings

Fig. 1 is the schematic diagram of the principle of the present invention to prepare fluorescent coded microspheres doped with europium ions;

Fig. 2 is the scanning electron micrograph of the macromolecule fluorescence coded microsphere doped with europium ion provided in Example 1 of the present invention;

Fig. 3 is the fluorescence spectrogram of the fluorescence coded microspheres of different europium additions provided in Example 1 of the present invention;

Fig. 4 is the average value and fluctuation range of the fluorescence emission intensity values of europium ions and PSDVB microspheres in fluorescently encoded microspheres with different europium additions provided in Example 1 of the present invention.

the

Detailed ways

The technical solutions of the present invention will be further described below in conjunction with the accompanying drawings and embodiments.

Example 1

This embodiment provides polymer fluorescently encoded microspheres doped with europium ions, and the preparation steps are as follows:

1. Preparation of Eu ³⁺ solution

Dissolve 0.0352 g of Eu ₂ O ₃ in 1 mL of CH ₃ COOH, make a 100 mL solution with deionized water, heat and shake to dissolve, and obtain a colorless and transparent Eu ³⁺ solution.

2. Preparation of polymer fluorescently encoded microspheres doped with europium ions

Add isopropanol to a 100mL Erlenmeyer flask: deionized water = 1:1 solvent 40mL, Eu ³⁺ solution (M _Eu = 0-20μmol), PSDVB microspheres 75㎎ (provided by Suzhou Nano Microbe Technology Co., Ltd. ), polyvinylpyrrolidone (PVP) 60㎎, placed in a high-temperature shaking incubator (set at 80°C, 220 rpm), and react at a constant temperature of 80°C for 3 hours. After the reaction, the mixture was centrifuged (2000 rpm), and then the microspheres were washed three times with deionized water (shock first: 1000 rpm, then centrifuge: 2000 rpm, remove the supernatant, and then deionized water repeated shaking and centrifugation), and then freeze-dried to obtain polymer fluorescent-encoded microspheres doped with europium ions.

Referring to accompanying drawing 1, it is the schematic diagram of the principle of the present invention to prepare the fluorescence coding microsphere doped with europium ion, wherein, I ₁ is the fluorescence emission intensity of PSDVB microsphere, and I ₂ is the fluorescence emission intensity of europium ion.

Referring to accompanying drawing 2, it is the scanning electron micrograph of the macromolecule fluorescent encoding microsphere doped with europium ion provided in this embodiment; As can be seen from Figure 2, the fluorescent encoding microsphere has regular appearance, uniform particle size, surface It is relatively smooth, with an average particle size of about 10 μM.

Referring to accompanying drawing 3, it is the fluorescence spectrogram of the fluorescent coding microsphere of different europium addition provided by the present embodiment; As can be seen from Fig. 3, along with the increase of europium addition, the fluorescence emission intensity of setting PSDVB microsphere unchanged, the fluorescence emission intensity of europium on the fluorescently encoded microspheres gradually increased.

Referring to accompanying drawing 4, it is the average value and fluctuation range of the fluorescence emission intensity ratio of europium ion and PSDVB microsphere in the fluorescence coding microsphere of different europium addition provided by the present embodiment, wherein, I ₁ is the fluorescence of PSDVB microsphere Emission intensity, _I2 is the fluorescence emission intensity of europium ions. It can be seen from Figure 4 that with the increase of the amount of europium added, the average value of the fluorescence emission intensity ratio (I ₂ /I ₁ ) of europium ions in the fluorescently encoded microspheres to the PSDVB microspheres gradually increases, and a set of different The average value of I ₂ /I ₁ is a group of coded microspheres.

Claims (2)

1. a high molecular fluorescent coding microball for europium doped ion, is characterized in that: its median size is 5～10 μ M, and maximum excitation wavelength is 300～350 nm left and right, and maximum emission wavelength is respectively near 395nm and 611nm.

2. a preparation method for the high molecular fluorescent coding microball of europium doped ion as claimed in claim 1, is characterized in that comprising the steps:

(1) by Eu ₂o ₃be dissolved in CH ₃in COOH, be made into Eu with deionized water ³⁺solution;

(2) taking polyvinylpyrrolidone as dispersion agent, the polystyrene-divinylbenzene crosslinked microsphere of sulfonic acid surfactant base is dispersed in mixed solvent, described mixed solvent is for by volume, Virahol: deionized water=1:1, and the concentration of europium ion in mixed solvent is 3.8 × 10 ^-3～7.6 × 10 ^-2mg/mL; The Eu that adds step (1) to obtain ³⁺solution, microballoon and Eu ³⁺mass ratio be 24:1～480:1; Be that under the condition of 70～90 DEG C, concussion is processed 0.5～5 hour in temperature, after centrifuge washing, lyophilize are processed, obtain the high molecular fluorescent coding microball of europium doped.